Article

pubs.acs.org/crystal

Direct Laser Writing of LaBGeO5 Crystal-in-Glass Waveguide Enabling

Frequency Conversion
Alexey S. Lipatiev,*,† Tatiana O. Lipateva,† Sergey V. Lotarev,† Andrey G. Okhrimchuk,†
Alexey S. Larkin,‡ Mikhail Yu. Presnyakov,§ and Vladimir N. Sigaev†
†
D. Mendeleyev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, Russia
‡
Lomonosov Moscow State University, Leninskie Gory GSP-1, 119992 Moscow, Russia
§
NRC Kurchatov Institute, Akademika Kurchatova pl. 1, 123182 Moscow, Russia
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ABSTRACT: We report on a technique of femtosecond laser-

induced crystallization of glass, allowing improvement in the
Downloaded via AMERICAN UNIV IN CAIRO on August 6, 2022 at 01:58:02 (UTC).

homogeneity of continuous crystalline tracks formed in lanthanum

borogermanate glass using a focused beam with the elliptical-shaped
waist cross section instead of a conventional circular one. Second
harmonic generation produced by near-infrared femtosecond laser
pulses was demonstrated in the waveguiding mode for the laser
written crystalline track. The structure of the fabricated single
crystalline waveguides is investigated with high resolution trans-
mission electron microscopy and micro-Raman spectroscopy.

■ INTRODUCTION
Femtosecond (fs) laser pulses possess extremely high peak
power, which made them a powerful tool for processing
transparent solid materials including high-temperature ones
such as oxide crystals and glasses.1 High light intensity around
∼1014 W/cm2 in the waist of the fs beam tightly focused in the
transparent dielectric material gives rise to multiphoton
absorption and avalanche photoionization transferring light
energy to any glass regardless of its absorbance at the
fundamental wavelength of the laser.
Controllable space-selective precipitation of microcrystals is a
promising type of laser-induced modification of glasses.
Methods of direct laser writing of 2D/3D amorphous or
crystalline architectures (dots, lines, arrays of crystals, single
crystal-like waveguides of a complicated shape) possessing
functional properties such as waveguide ones, second-harmonic
generation (SHG), and luminescence have been recently
developed.2−8 Space-selective growth of lines consisting of
nonlinear optical crystals in glasses was widely studied by T.
Komatsu and co-workers4−6 who developed techniques of
laser-induced crystallization of glasses doped with rare-earth or
transition metal ions by the continuous wave (cw) laser beam.
In addition to surface glass crystallization they have recently
succeeded in cw laser patterning of highly orientated β-BaB2O4
crystals inside the glass fiber.9
A number of significant studies in the field of laser-induced
crystallization of glass have been carried out on lanthanum
borogermanate (LBG) glasses10−12 including 3D space-
selective glass crystallization by fs lasers.11,12 The interest for
LBG glass is specified by the opportunity to precipitate
ferroelectric LaBGeO5 crystals with the stillwellite structure
(space group P31) on the glass surface as well as in the glass
bulk initiating second-order optical nonlinearity.13,14 Laser-
induced space-selective crystallization of glass opens the
prospect for direct laser writing of three-dimensional active
crystalline waveguides for fabrication of novel functional
components for integrated optics, optoelectronics, and
photonics.15 Nevertheless, until recently no studies concerning
the characterization of waveguiding properties of crystalline
tracks fabricated in glass had been reported. In 2012 Feng et
al.16 carried out preliminary investigations on the waveguiding
behavior of crystalline tracks recorded by UV laser beam on the
surface of ribbon (La,Yb)BGeO5 glass fiber. The optical loss of
the crystalline waveguide was estimated as 3 dB/cm from
scattered light measurement, but no detectable SHG was
demonstrated in the waveguide output.
H. Jain’s group proposed an aberration correction method via
modification of the laser beam by a spatial light modulator
(SLM) for improvement of the laser-written crystalline line
cross-section shape in 25La2O3·25B2O3·50GeO2 glass in order
to make it more suitable for waveguide applications.17 Recently
this method was successfully applied to provide waveguiding
properties of the laser-written LaBGeO5 crystal-in-glass
channels and to fabricate symmetric crystal junctions by laser
beam single-pass writing. The single crystal nature of the laser-
written waveguides was proven and optical losses for the single-
crystal architectures inside glass were shown to be no higher
than 2.64 dB/cm at 1530 nm.15
Received: April 24, 2017
Revised: July 11, 2017
Published: July 25, 2017

© 2017 American Chemical Society 4670 DOI: 10.1021/acs.cgd.7b00581

Cryst. Growth Des. 2017, 17, 4670−4675
Crystal Growth & Design
In the present study we demonstrate an approach to fs laser-
induced crystallization of glass using a laser beam with an
elliptical cross section of the waist that improves the
homogeneity of written crystalline tracks. Second harmonic
generation in the waveguiding mode has been shown in the
laser-written waveguides for the first time to the best of our
knowledge.
■ EXPERIMENTAL SECTION
The LBG glass of the 25La2O3·30B2O3·45GeO2 molar composition
slightly shifted from that of LaBGeO5 crystal was fabricated by
conventional melt-quenching technique in a platinum crucible.
Selected glass composition enables some decrease in the glass
crystallization ability as compared with the glass of 25La2O3·25B2O3·
50GeO2 molar composition used in previous studies10−12,15 and
fabrication of a glass of improved homogeneity in the cylindrical mold
with a diameter of 3 cm and height of 5 cm. As-quenched glass
samples were annealed for 2 h at 630 °C. All glass samples were
thoroughly laser-grade polished with diamond suspension to meet a
requirement of elimination of surface scattering and the laser beam
distortion.
The Yb-base femtosecond laser system with a regenerative amplifier
was used for direct laser writing of crystalline tracks by pulses with 300
fs duration at the wavelength of 1030 nm and a pulse repetition rate up
to 200 kHz. The laser beam was focused through Olympus 50×
objective lens (N.A. = 0.65) at the depth of 170 μm below the glass
surface. Experiments using Olympus objective lens with N.A. of 0.45
were also performed to compare the crystal morphology written by the
beam focused with different N.A. by polarized optical microscopy. The
pulse energy was varied in the range of 0−20 μJ by an attenuator
consisting of a half-wave plate and a Glan prism. M2 factor of the laser
beam was less than 1.3, and beam diameter was about 4.5 μm. The
main driving force of glass crystallization is a heat transfer due to high
temperature gradient induced by local nonlinear absorption of the fs
laser beam. In order to reduce Kerr self-focusing and get anisotropic
temperature gradient in the beam waist region we applied inscription
by the laser beam with the elliptical waist cross section.18 We tested
three different methods for the laser beam transformation to
accomplish this, including conversion of the Gaussian laser beam
having axial symmetry into a beam with an elliptical or quasi-elliptical
cross section by letting it pass through (1) an anamorphic prism pair
(anamorphic magnification 2.5) or (2) a slit (0.42 mm width); (3)
introducing astigmatism into the beam by a cylindrical lens ( f = −400
mm). The beam was focused by high N.A. objective lenses after
passing these elements, which broke its axial symmetry. The calculated
beam waist diameter for the objective lens of N.A. = 0.65 and 0.45 was
equal to 2.3 and 3.3 μm, respectively. The anamorphic prism pair, the
cylindrical lens, or the slit was oriented so as to stretch the beam waist
cross section along the laser beam scanning direction up to 2.5, 8, and
10 times, respectively. The proposed technique was previously used for
efficient homogeneous refractive index modification and waveguide
writing in crystal media18,19 and our group tested it for laser-induced
crystallization of LBG glass.20
The computer-controlled high-precision motorized stage based on
stepping motors was used for translating the glass sample relative to
the focused laser beam. A live view of the laser writing process
important for a real-time inspection of the forming structures was
captured by CMOS camera. Crystal growth under the laser beam
could be detected in situ due to noticeable SHG in the precipitating
LaBGeO5 crystalline phase.
Olympus BX-51 optical microscope was used for to analyze the
morphology of the crystalline tracks. Identification of the microcrystal
type and its orientation was performed using a polarizing confocal
micro-Raman spectrometer included in NTEGRA Spectra nano-
laboratory (NT-MDT Co.). An argon ion laser with a wavelength of
488 nm was used as the excitation source and the beam diameter at the
focus was about 1 μm. A polarized Raman spectra mapping was
performed by scanning areas of crystalline tracks from point to point
with the step of 0.8 um.
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Article
A layout of the experimental setup applied for measurement of
optical propagation loss in crystalline waveguides and SHG signal
registration is shown in Figure 1.
Figure 1. Experimental setup of the propagation losses measurements
and SHG detecting.
To observe the waveguiding effect and to measure propagation
losses, we polished the facets perpendicular to crystalline waveguides
after laser-induced crystallization and removed the ends of the laser-
written crystalline track. So by the moment of optical loss analysis, the
start point and the end point of the waveguide had the same structure
as other parts of the waveguide. We used pulses attenuated and
stretched to 600 fs duration at pulse repetition rate of 10 kHz as input
light for measurement of light transmittance of crystalline waveguides.
They were focused into waveguide input end by an objective lens with
N.A. of 0.1 aligned by 6-axis translation table for light coupling. The
sample with crystalline waveguides was set on 3-axis adjustable glass
sample holder. Ophir PD-30R power meter head was used for
measurement of output power of light passed the waveguide. SHG
signal measurement was made with the same setup. We inserted a
visible filter in front of the power meter and used a spectrometer ASP-
150 with Czerny-Turner optical circuit for analyzing SHG spectrum of
the output. The laser beam profiler (Ophir Spiricon SP 620U)
replacing the power meter head was used to study crystalline
waveguide propagation modes.
A detailed analysis of a longitudinal cross section of crystalline
waveguides formed in the LBG glass was performed by means of
transmission electron microscopy (TEM) using Titan 80-300 S/TEM
system (FEI). TEM images were obtained in 300 kV mode also by
using of STEM bright-field (BF) and high angle annular dark-field
(HAADF) detectors. A longitudinal cross-section slice was prepared as
a specimen for TEM analysis by ion beam etching.
■
RESULTS AND DISCUSSION
As in previous studies,15,17 the formation of crystalline tracks
under fs laser writing started from the growth of the crystal seed
from which a crystal of predetermined length was later grown
by moving the sample relative to the focused laser beam. The
appearance of the crystal seed was detected by the SHG effect
due to the second-order nonlinear optical response of the
LaBGeO5 phase. While the average power of the laser beam is
constant, the dependence of the crystal seed appearance time
on the laser pulse energy has an exponential character.21
However, the crystal seed nucleation process has a statistical
nature due to fluctuations in the glass composition.21,22 Even a
slight reduction of pulse energy can cause a significant increase
of the crystal seed formation time. We have proposed an
optimized technique of laser-induced nucleation of a crystalline
seed, ensuring its steady growth time. The technique
constitutes a gradual increase of the laser pulse energy at a
constant rate during glass exposure by focused laser beam until
the appearance of the microcrystal seed. It is based on the
assumption that crystal seed growth occurs at the interface
between glass melt in the region of the beam waist and glass
heated above the glass transition temperature due to the heat
transfer. The increase of the laser pulse energy results in
movement of the glass melt-heated glass interface and growth
of the initial nanometer-sized seed to the microcrystal seed
DOI: 10.1021/acs.cgd.7b00581
Cryst. Growth Des. 2017, 17, 4670−4675
Crystal Growth & Design Article

Figure 2. Typical polarized Raman spectra (a) and crossed-polarized optical microscope images of crystalline tracks written by the Gaussian beam
with axial symmetry (b), by the laser beam with elliptical cross section of the waist formed with the negative cylindrical lens (c), anamorphic prism
pairs (d), and the slit (e). Optical transmission micrographs of crystalline waveguide cross section and maps of integral intensity in the range of 384−
404 cm−1 of polarized Raman spectra registered in the Z(XX)Ż geometry are shown on the insets. The laser beam scanning and incidence direction
are indicated by arrows v and k, respectively. The laser beam scanning speed and pulse energy for crystal growth (b−e) were 45 μm/s, 0.9 μJ; 40
μm/s, 2.1 μJ; 40 μm/s, 0.9 μJ; and 42 μm/s, 2.3 μJ, respectively.

possessing strong SHG activity that coincides with previously
obtained data on crystallization of BaO-TiO2-GeO2 glass using
a fs laser.23 The proposed technique enables reduction of the
crystal seed formation time as compared to irradiation by the
laser beam with constant pulse energy and determines the pulse
energy close to optimal one for writing crystalline waveguide
structures.
The Raman spectra and top views of the crystalline tracks
inscribed in LBG glass by the circular and elliptical laser beam
waists are shown in Figure 2. The crystalline nature of obtained
tracks was checked for several regions throughout the entire
length of the tracks, and optical axis c orientation coinciding
with the laser beam scanning direction was confirmed by
polarized Raman spectra (Figure 2a). In addition, Raman
spectra mapping of crystalline tracks was performed for the area
of 384−404 covering a peak at 394 cm−1 that is characteristic
for LaBGeO5 single crystal when the c-axis is in the polarization
plane of excitation and detection radiation.24 It was determined
that the Raman spectra map for the crystalline track grown by
elliptical laser beam waist is almost identical to the one for the
crystalline track grown by the Gaussian laser beam (Figure 2b,c,
insets) and all Raman spectra maps are in good agreement with
results obtained earlier.11
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All crystalline tracks are colored when viewed in crossed
polarizers due to their strong birefringence (Figure 2b−d). It is
evident that crystalline waveguides formed by elliptical laser
beam waist in contrast to ones written by the Gaussian laser
beam have a more uniform distribution of retardance produced
by birefringence indicating that orientation and thickness of the
crystal in the track cross section are unchanged along a
waveguide. This result is similar to one obtained for the single
crystal-like waveguides formed by the SLM-corrected laser
beam.15 The self-focusing critical power is 0.94 MW, as
calculated by the formula25
Pcr_G = λ 2 /(2πn0n2) (1)
where λ is laser wavelength, and n0 and n2 are the linear and
nonlinear refractive index of LaBGeO5 crystal according to refs
16 and 26. Pulses with energies of hundreds of nanoJoules and
duration of 300 fs, which is necessary for local heating and
crystallization of glass, have a peak power of more than 3 MW
that is high enough to cause Kerr self-focusing of the Gaussian
beam. The self-focusing distorts the beam, causes filamentation,
and disrupts the uniformity of the cross-section shape of the
crystalline track. An optical transmission micrograph of a cross
section of the crystalline waveguide written by Gaussian beam
DOI: 10.1021/acs.cgd.7b00581
Cryst. Growth Des. 2017, 17, 4670−4675
Crystal Growth & Design
(Figure 2, inset) shows a significant elongation of the crystal
track at the bottom confirming the self-focusing phenomenon.
The beam with the elliptical beam waist has increased the
critical power of self-focusing that facilitates more uniform and
deterministic absorption of the laser beam.18 The proposed
technique is technically simpler than those based on high-cost
SLM and also provides more uniform local heating which
results in sustainable growth of a uniform crystal track with a
cross-section shape closer to the circular one.
Optical microscopy is not sufficient for general character-
ization of crystal quality of a crystalline track. Taking into
account that the track length exceeds several millimeters, such
characterization can take a long time. Considering this point,
we estimated the optical propagation losses of obtained
waveguides of about 9.1 mm length, which appears to be
very sensitive to crystal structure quality. We used the direct
method of measurement of the propagation loss (PL) (Figure
1). The power of the beam which passed the optical system
with (Ps) and without the sample (P0) was measured, and then
the propagation loss was calculated by the formula, taking into
account the Fresnel reflection losses at both ends of the
waveguide
PL = −10/l × lg(Ps/P0/Ts ) 2
(2)
where l is a length of the waveguide (cm) and Ts is a Fresnel
transmission coefficient determined as
Ts = 4n0 /(n0 + 1)2 (3)
Due to the poor quality of crystal tracks formed by the
Gaussian beam waist, we did not find waveguiding with them.
In contrast, we observed multimode waveguiding behavior for
the crystalline track (Figure 3) written by elliptical beam waist
Figure 3. Optical transmission micrograph of crystalline waveguide
cross section (a) and waveguide fundamental (b) and SHG (c) mode
intensity distribution at the output end of the waveguide.
with propagation loss estimated as less than 3.1 dB/cm at the
wavelength of 1030 nm. These propagation losses are of an
order of magnitude comparable to the ones obtained for single
crystal waveguides.15
SHG in crystalline waveguide written using the anamorphic
prism pair was detected (Figure 3c). The dependence of SHG
intensity on laser beam input power follows quadratic power
law I2ω ∼ Iω2, which corresponds to the regime of low
conversion coefficient (Figure 4).
The calculated value of SHG conversion efficiency was found
to be as high as ∼0.91%/W, taking into account the
transmission of visible filter and Fresnel reflections of both
ends of the crystal waveguide. The measurable value of the
conversion coefficient indicates that there is a phase matching
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Figure 4. Dependence of the SHG intensity on the input radiation
power. Inset shows the SHG spectrum at the crystalline waveguide
output.
condition for SHG. The angle of collinear phase matching in
LaBGeO5:Nd3+ single crystal is nearly 54°.27 Obviously, the
collinear phase matching is unlikely to take place in the laser-
written crystalline waveguide because the polar axis of the
LaBGeO5 phase coincides with the waveguide axis. The
birefringence-induced noncollinear phase matching is moreover
impossible because it requires even higher propagation angles
with respect to the optical axis. One of the mechanisms which
can be assumed for significant SHG activity of the crystal
waveguide is the Cherenkov-type phase matching, which was
found for LaBGeO5 single crystal.28 SHG with this type of
phase matching could have significant efficiency in a multimode
waveguide, because, for example, the waveguide could ensure
overlap between the IR fundamental mode and a higher order
mode of the second harmonic, that is required for Cherenkov-
type phase matching conditions.29 SHG under the condition of
phase matching between different transverse modes assumes
that light of fundamental and second harmonic frequencies
belongs to different transverse modes. This circumstance is
reflected in Figure 3b,c, where maxima of intensity distributions
of fundamental and SHG light are positioned in different sites
of the crystalline waveguide output.
A more detailed analysis of the waveguide crystal structure
was performed by means of TEM. For this purpose a
longitudinal slice of the crystal waveguide (Figure 2d) was
cut from its cross section and polished by argon ion beam.
TEM (Figure 5) reveals an asymmetric crystal growth
exhibiting the one-sided peripheral part with single crystal
nature and the central part of crystal waveguide at first view
resembling the LaBGeO5 structure resulting from grain-
oriented crystallization of LBG glass.30 However, the crystal
phase in the central part of the waveguide virtually does not
change its polar axis orientation. It remains very close to the
laser scanning direction which is confirmed by diffraction
pattern (ICDD #39262, the angle of crystal disorientation is
less than 4°). Despite this, all parts of the crystal waveguide
have a well-formed crystal lattice (Figure 5b), but the revealed
grain boundaries can greatly influence propagation loss.
Thus, TEM data discover a complex crystal growth dynamics
due to the considerable difference between temperature
distribution in beam waist and periphery region during laser
irradiation of LBG glass. The problem of single crystal
DOI: 10.1021/acs.cgd.7b00581
Cryst. Growth Des. 2017, 17, 4670−4675
Crystal Growth & Design
Figure 5. (a) STEM HAADF image of the lateral slice of the laser-induced crystalline waveguide and diffraction patterns of its different parts
corresponding to LaBGeO5 crystal oriented on the laser scanning direction. Arrows v and k show directions of laser scanning and laser beam
propagation, respectively. (b) HR TEM image of crystal lattice typical for all parts of the crystalline waveguide.
formation and optical loss reduction is still challenging and
requires more precise control of spatiotemporal characteristics
of the laser beam.
■
SUMMARY
In conclusion, we propose a technique improving the
morphology of the fs laser-induced crystalline track in the
LBG glass by means of applying the laser beam with an
elliptical cross section of the waist, whose larger diameter is
aligned along the writing direction. This technique enables
writing a crystalline waveguide with propagation loss less than
3.1 dB/cm at the wavelength of 1030 nm. The second
harmonic generation in the crystalline laser-written waveguide
is demonstrated for the first time. TEM analysis shows that the
structure of LaBGeO5 crystalline phase forming waveguides
contains the homogeneous periphery region with the
orientation of the polar axis aligned exactly along the laser
beam scanning direction and the central region formed by
needle-like crystals growing simultaneously with the homoge-
neous region under the polar axis orientation within 4° of the
waveguide direction. Further investigation of the influence of
spatiotemporal characteristics of the laser beam on the laser-
induced crystal structure is required for improving its
crystallinity and homogeneity and reducing the propagation
loss of the crystal-in-glass waveguide.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: lipatievas@yandex.ru.
ORCID
Alexey S. Lipatiev: 0000-0002-4122-7979
Sergey V. Lotarev: 0000-0003-0885-3609
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work has been supported by the Russian Foundation for
Basic Research (grants 16-33-60081, 16-33-01050, 16-03-
00541) and the Ministry of Science and Education of Russia
(grant 14.Z50.31.0009).
■
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4675 DOI: 10.1021/acs.cgd.7b00581

Cryst. Growth Des. 2017, 17, 4670−4675